S,S-dialkyl-N-substituted phosphoroamidodithionites

ABSTRACT

Compounds of the formula   WHEREIN R1 and R2 are independently alkyl of 1 to 8 carbon atoms, or alkenyl of 2 to 8 carbon atoms, R3 is hydrogen or alkyl of 1 to 4 carbon atoms, and R4 is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, acryl of 6 to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of 1 to 4 carbon atoms or an acyl group of 2 to 4 carbon atoms, with the proviso that R3 and R4 may be joined to form an alkylene radical of 2 to 5 carbon atoms. The compounds possess insecticidal and herbicidal activity.

United States Patent Freenor, III

[ S,S-DIALKYL-N-SUBSTITUTED PHOSPHOROAMIDODITHIONlTES [75] Inventor:Francis J. Freenor, Ill,

Richmond, Calif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

[22] Filed: May 2, 1974 [21] Appl. No.: 466,433

Related US. Application Data [62] Division of Ser. No. 219,559, Jan. 20,1972, Pat. No.

[52] US. Cl 260/959; 260/247.l R [5 l] Int. Cl C07f 9/24; AOln 9/36 [58]Field of Search 260/959 [56] References Cited UNITED STATES PATENTS2,995,596 8/1961 Debo et al. 260/959 X Primary Examiner-Anton H. SuttoAttorney, Agent, or Firm-G. F. Magdeburger; Dix A. Newell; RaymondOwyang [4 1 May 27, 1975 [57] ABSTRACT Compounds of the formula whereinR and R are independently alkyl of l to 8 carbon atoms, or alkenyl of 2to 8 carbon atoms, R is hydrogen or alkyl of l to 4 carbon atoms, and Ris hydrogen, alkyl of l to 4 carbon atoms, alkenyl of 2 to 4 carbonatoms, acryl of 6 to 15 carbon atoms optionally substituted with halogenatoms or alkyl groups of l to 4 carbon atoms or an acyl group of 2 to 4carbon atoms, with the proviso that R and R may be joined to form analkylene radical of 2 to 5 carbon atoms, The compounds possessinsecticidal and herbicidal activity.

9 Claims, N0 Drawings 1 S,S-DIALKYL-N-SUBSTITUTEDPHOSPHOROAMIDODI'IHIONITES This is a division of application Ser. No.219,559, filed Jan. 20, I972, now US. Pat. No. 3,832,424

BACKGROUND OF THE INVENTION Field The present invention is directed tophosphoroamidodithionites, more particularly S,S-dialkyl- N-monoanddi-substituted phosphoroamidothionites and their use as insecticidesand/or herbicides.

DESCRIPTION OF THE INVENTION Compounds of the present invention may berepresented by the formula R S R P ll R I R wherein R and R areindependently alkyl of 1 to 8 carbon atoms, preferably alkyl of l to 4carbon atoms and more preferably alkyl of 3 to 4 carbon atoms, oralkenyl of 2 to 8 carbon atoms, preferably alkenyl of 2 to 4 carbonatoms, R, is hydrogen or alkyl of l to 4 carbon atoms, R, is hydrogen,alkyl or 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6to 15 carbon atoms substituted with O to 5 halogen atoms of atomicnumber 9 to 35 or alkyl groups of l to 4 carbon atoms, or an acyl groupof 2 to 4 carbon atoms, with the proviso that R and R may be joined toform an alkylene radical of 2 to 5 carbon atoms, preferably 4 to 5carbon atoms.

The aryl groups which R, may represent are preferably benzyl or phenyl,either being substituted with to halogen atoms of atomic number 9 to 35or alkyl groups of l to 4 carbon atoms. More preferably, R is phenylsubstituted with 0 to 2 halogen atoms of atomic number 9 to I7 or alkylof l to 2 carbon atoms, and still more preferably, phenyl substitutedwith 0 to I chlorine or fluorine atom.

Representative alkyl groups which R R R and R may represent includemethyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. Representativealkenyl groups which R R and R may represent include vinyl, allyl,crotyl, etc. R and R may also be pentyl, hexyl, octyl, etc. PreferablyR, and R will be the same, or will be alkyl. R is preferably alkyl oraryl optionally substituted as the case may be.

Representative aryl groups which R may represent include phenyl,naphthyl, benzyl, o-chlorophenyl, ofluorophenyl, o-bromophenyl,p-fluorophenyl, mchlorophenyl, o-methylphenyl, p-butylphenyl,obutylphenyl, 0,p-dichlorophenyl, pentachlorophenyl,o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronaphthyl, etc.

Representative radicals which R and R joined together with nitrogen mayrepresent include piperidyl, pyrrolidyl and morpholine.

Representative acyl groups which R may represent include acetyl,propionyl and butyryl.

Representative compounds of the present invention includeS,S-dimethyl-N-butyl phosphoroamidodithionite, S,S-dimethyI-N-phenylphosphoroamidodithionite, S,S-diethyl-N,N-dimethylphosphoroamidodithionite, S,S-dimethyl-N-acetylphosphoroamidodithionite,

2 S-methyl-S-ethyl-N-isopropyl phosphoroamidodithionite,S-methyl-S-ethyl-N-vinyl phosphoroamidodithio nite,S,S-diethyl-N,N-diethyl phosphoroamidodithionite,S,S-diisopropyl-N-methyl phosphoroamidodithionite, S,S-n-butylphosphoroamidodithionite, S-methyl- S-hexyl-N-ethyl-N-propionylphosphoroamidodithionite, S-propyl-S-allyl-N-methyl-N-phenylphosphoroamidodithionite, S-methyl-S-vinyl-N-methylphosphoroamidodithionite, S,S-dipropyl-N-2- chlorophenylphosphoroamidodithionite, S,S-dibutyl- N-2,4-dichlorophenylphosphoroamidodithionite, S,S-dibutyI-N-Z-ethylphenylphosphoroamidodithionite, S,S-diethyl-N-ethyl-N-2-naphthylphosphoroamidodithionite,S,S-dibutyl-N-pentachlorophosphoroamidodithionite,S,S-dibutyl-N-2,4-dichloro-3,5- dimethylphenyl phosphoroamidodithionite,S,S-dibutyl-N-piperidyl phosphoroamidodithionite, S,S dibutylN-pyrrolidyl phosphoroamidodithionite, etc.

The compounds of the present invention are prepared by the reaction ofan appropriate S,S-dialiphatic hydrocarbyl phosphorus halide withammonia with a suitable amine or with an appropriate amide according tothe following reaction:

R S R P X HN R S t R R S R P N HX R 3 R wherein R R R and R are asindicated above and X is a halogen, preferably chlorine.

Generally, the reaction is accomplished by adding the ammonia or amineslowly to the phosphorus chloride. Preferably an excess, e.g., up totwice the molar amount of ammonia, amide or the amine can be used. Theexcess reactant acts as a base acceptor to react with the evolved HX andthereby neutralize it. The reaction is preferably carried out in thepresence of an inert solvent, such as methylene chloride ether, benzene,hexane, etc. Also a molecular seive is preferably present which servesas a drying agent for the solvent amine. The amount of molecular seiveshould be enough to assure substantially complete removal of any H20.

When ammonia is reacted with the phosphorus chloride it is generallypreferable to dissolve the ammonia in the solvent and then add thephosphorus chloride to the ammonia-solvent mixture. When an amine isused, the solvent is preferably added to the phosphorus chloride and theamine added slowly to the phosphorus chloride-solvent mixture.

The above reaction is preferably carried out at a temperature from 78 to30C. Following the reaction, the product can be recovered byconventional means. Thus the reaction mixture may be stripped ofsolvent, the product washed with water and dried over magnesium sulfate.

The phosphorus chloride is known in the art and can be prepared as forexample by the procedure in US. Pat. No. 3,210,244. Thus a suitablemercaptan may be EXAMPLE 1 Preparation of S,S-di-n-buty1phosphoroamidodithionite Ammonia (large excess based on the amount of8,8- dibutyl phosphorus chloride) was dissolved in methylene dichloride,cooled to dry ice temperature. A small number of molecular sieves wereadded. S,S-dibutyl phosphorus chloride, 6.5 g. (0.03 mole), was thenadded slowly. A solid white precipitate resulted. The reaction mixturewas slowly warmed up to room temperature and left standing approximately48 hours. The white solid was removed and the remaining solutionstripped to obtain an oil having the following analysis:

Calculated Found EXAMPLE 2 Preparation of S,S'di-n-buty1-N,N-diethylphosphoroamidodithionite 100 ml. of methylene dichloride plus a smallamount of molecular sieves were mixed with 13.05 g. of S,S-din-butylphosphorus chloride. Diethyl amine (7.8 g.)

was added slowly. The resulting slurry was allowed to stand forapproximately 24 hours. The resulting mixture was filtered and strippedto obtain a colorless oil which on chemical analysis showed:

S,S-di-n-butyl N-pyrrolidyl phosphoroamidodithionite 5.84 g. (0.024mole) of S,S-di-n-buty1 phosphorus chloride was dissolved inapproximately 150 ml. of methylene dichloride. A small number ofmolecular sieves were added. Piperidine, 4.06 g. (0.05 mole) was addedslowly. The reaction mixture was cooled in an ice bath during thereaction. The reaction mixture was permitted to stand overnight afterwhich it was filtered and evaporated down to obtain a yellow oil whichwas then dissolved in methylene dichloride, washed twice with water anddried over magnesium sulfate. After isolation, the chemical analysisshowed:

Calculated Found EXAMPLE 4 Preparation of S,S-di-n-buty1-N-acety1phosphoroamidodithionite Under a nitrogen atmosphere ml. of diethylether was dried over several molecular sieves. Then, 9.15 g. (0.0373mole) of S,S-di-n-buty1 phosphorus chloride was added to the dry ether.Next, 2.21 g. (0.0373 mole) of acetamide was added and the reactionmixture turned cloudy. Triethylamine, 3.78 g. (0.0373 mole) was addeddropwise. A white precipitate formed, and the reaction mixture wasstirred for 1 hour at ambient temperature. After warming, the reactionmixture was stirred for 24 hours.

The white precipitate was removed by filtration. The resulting solutionslowly formed two layers. After 30 days the layers were separated. Theupper layer weighed 5.30 grams. Analysis:

Calculated Found TABLE 1 Elemental Analysis 1:

Ex. P Halogen No. Compound Calculated Found Calculated Found CalculatedFound 5 S,S-n-butyl-N,Ndi-n-propy1 20.7 20.7 10.0 10.0

phosphoroamidodithionite 6 S.Sdi-n-buty1 N,N-dimethyl 25.3 25.1 12.211.8

phosphoroamidodithionite 7 S,S-di'n-buty1-N-methyl 5.8 5.3

phosphoroamidodithionite 8 S ,S-di-n-butyl N ,N-di-n-butyl 19.0 19.0 9.28.8

phosphoroamidodithionite 9 S,S-diisopropyl-N,N'diethyl 12.2 11.8

phosphoroamidodithionite 10 S,S diisopropyl-N.N-di-N-propyl 22.8 22.3 11.0 10.6

phosphoroamidodithionite 1 1 S.S-di-n-buty1-N-4-ch1oropheny1 10.6" 10.5"

phospho roamidodithionite 12 S,S-di-n-butyLN-Z-t'luorophenyl 6.0 6.2"

phosphoroamid odithionite 14 S,S-diisopropy1N-2-11uoropheny1 22.0 21.811.6 1 1.0

pho sphoroamidodithionite 15 S.S-diisopropyl-N.N-di-n-butyl 20.7 18 .610.0 9 2 phosphoroamidodithionite The compounds of the present inventionare, in general, herbicidal in both preand post-emergence applications.For pre-emergence control of undesirable vegetation these compounds willbe applied in herbicidal quantities to the environment, cg, soilinfested with seeds and/or seedlings of such vegetation. Suchapplication will inhibit the growth of or kill the seeds, germi natingseeds and seedlings. For postemergence applications the compounds of thepresent invention will be applied directly to the foliage and otherplant parts. Generally they are effective against wced grasses as wellas broadleaved weeds. Some may be selective with respect to type ofapplication and/or type of weed.

Preand post-emergence herbicidal tests on representative compounds ofthis invention were made using the following methods:

Pre-Emergence Test An acetone solution of the test compound was preparedby mixing 750 mg. compound, 220 mg. ofa nonionic surfactant and 25 ml.of acetone. This solution was added to approximately 125 mi. of watercontaining 156 mg. of surfactant Seeds of the test vegetation wereplanted in a pot of soil and the compound solution was sprayed uniformlyonto the soil surface at a dose of lOO micrograms per cm The pot waswatered and placed in a greenhouse. The pot was watered intermittentlyand was observed for seedling emergence, health of emerging seedlings,etc. for a 3-week period. At the end of this period the herbicidaleffectiveness of the compound was rated based on the physiologicalobservations. A to 100 scale was used; 0 representing no phytotoxicity,100 representing complete kill.

10 Post-Emergence Test The test compound was formulated in the samemanner as described above for the pre-emergence test. The concentrationof the compound in this formulation was 5000 ppm. This formulation wasuniformly sprayed on 2 replicate pots of 24-day-old plants(approximately 15 to 25 plants per pot) at a dose of lOO micrograms percm After the plants had dried, they were placed in a greenhouse and thenwatered intermittently at their bases as needed. The plants wereobserved periodically for phytotoxic effects and physiological andmorphological responses to the treatment. After 3 weeks the herbicidaleffectiveness of the compound was rated based on these observations. A Oto I00 scale was used; 0 representing no phytotoxicity. 100 representingcomplete kill.

The results of these tests appear in Table II.

TABLE II Compound S S-dinbutyI-N.N-diethyl phosphoroarnidodithionite SS-n-butyl-N N-di-n-propyi phosphoroamidodithionite S,S-din-butyl-N,N-dimethyl phosphoroamidodithionitc S,S-di-n-butylphosphoroamido dithionite S,Sdin-butyl-Nmethyl phosphoroamidodithioniteS S-di-n-butyl-N,N-di-n-butyl phosphoroamidodithionitcS,S-diisopropyl-N,N-diethyl phosphoroamidodithionite S,S-diisopropylN,N-di-n-propyl phosphoroarnidodithionite S,S-di-n-butyl-N-2-fluorophenyiphosphoroamidodithionite S.S-diisopropyLMH-di'n-butylphosphoroamidodithionite S,S-diisopropyl phosphoroamidodithioniteS,S-diisopropyl-N-methyl phosphoroamidodithionite S,Sdi-nbutylN-pyrrolidyl phosphoroamidodlthionite S ,S-diisopropyl-Ncthylphosphoroamidodithionite S,S-diisopropyl-N-n-butylphosphoroamidodithionite S,Sdi n'octyl-N-methyl phosphoroamidodithioniteS S-di-noctylNpiperidyl phosphoroamidodithionite HerbicidalEffectiveness 0 w C M P L 93/85 loo/100 /100 100/100 100/I00 /!O0 1100/lUO -/i00 /i00 /100 -ls5 ---/s0 -195 -rs5 -/05 /90 90% so/ioo 75 TABLEll Continued Herbicidal Effectiveness Compound 0 S,S-diethyl-N-N-diethyl/9O phosphoroamidodithionite phosphoroam idodithionite sfi'diethyl-NN-dimethyl phosphoroamidodithionite S,S-diethyl-N-ethylphosphoroamidodithionite phosphoroamidodithionite S,S-cli-n-propyl-Nacetyl 100/- 100/- phosphoroamidodithionite S,S-di-i-propyl-N-butyrylphosphoroamidoditionite S,S-di-i-propyl N-acetyl 85/phosphoroamidodithionite phosphoroamidodithionitephosphoroamidodithionite phosphnoroamidodithioniteS,S-di-n-propyl-N-piperidyl /85 /80 phosphoroamidodithioniteS,S-di-n-propyl-N-methyl 100/ 80/85 phosphoroamidodithionitephosphoroamidodithionite S.S-di-n-propyl-N-benzylphosphoroamidodithionitc S,S di-n-propyl-N-al|ylphosphoroamidodithionite phosphoroamidodithioniteS,S-di-n-butyl-N-propionyl phosphoroamidodithionitephosphoroamidodithionite The amount of compound administered will varywith the particular plant part or plant growth medium which is to becontacted, the general location of application, i.e., sheltered areassuch as greenhouses as compared to exposed areas such as fields, as wellas the desired type of control. For pre-emergent control of most plantsdosages in the range of about 0.5 to 20 lbs. per acre will be used. Suchadministration will give a concentration of about 2 to ppm. compounddistributed throughout 0.1 acre-foot. For post-emergence application,such as foliar spray application, compositions containing about 0.5 to 8lbs. compound per 100 gal. spray will be used. Such application isequivalent to about 0.5 to 20 lbs. compound per acre.

The herbicidal compositions of this invention comprise a herbicidalamount of one or more of the above described compounds intimatelyadmixed with a biologically inert carrier. The carrier may be a liquiddiluent such as water or acetone or a solid. The solid may be in theform of dust powder or granules. These compositions will also usuallycontain adjuvants such as a wetting or dispersing agent to facilitatetheir penetration into the plant growth media or plant tissue andgenerally enhance their effectiveness. These compositions may alsocontain other pesticides, stabilizers, conditioners, fillers and thelike.

0 The compounds of the present invention also possess Test ProceduresTwo-spotted Mites (Tetranychus urticae): An acetone solution of thecandidate toxicant conmersed in the toxicant solution and then allowedto dry at room temperature for seven days at 85F. On the eighth day theegg mortality was rated on a scale of to l l; 0 representing no kill, 1l representing 100% kill.

Aphids (Aphis gossypii Glover):

An acetone solution of the candidate toxicant contaming a small amountof nonionic emulsifier was diluted with water to ppm. Cucumber leavesinfested with the cotton aphids were dipped in the toxicant solution.Mortality readings were then taken after 24 hours.

TABLE III Control Tw0-spotted Two-spotted Mites Compound Mites EggsAphids S,S-di-n-butyl-N,N-dimethyl 96 phosphoroamidodithionite$.S-n-butyLN,Ndi n-propyl IOO phosphoroamidodithionite S,S-di n-buty| 98phosphoroamidodithionite S,S-di-n-butylN-methyl 99 99phosphoroamidodithionite S,S-di-nbutyl-N-2-fluorophenyl 96phosphoroamidodithionite S,Sdiisopropyl-N-methyl 98phosphoroamidodithionite S,S-diisopropyl-N-ethyl lOO 96phosphoroamidodithionite S,Sdiethyl-N-ethyl phosphoroamidodithioniteS,S-di-n'propyl-N,N-diethyl 97* I00 phosphooamidodithioniteS,S-di-n-propy]-N,N-dimethyl lOO 100 phosphoroamidodithioniteS.S-di-n-pr0pyl-Nmethyl 100 phosphoroamidodithioniteS,Sdi-n-propyl-N-piperidyl H30 96 phosphoroamidodithioniteS,S-di-n-propyl-N N-di-n-propyl 99 99 phosphoroamidodithioniteS,S-di-n-propyl-N-benzyl 100 99 phosphoroamidodithionite S,S-di-n-propyl-N-allyl v 99 phosphoroamidodithionlte S,S-di-n-propyl-N-Z-fluorophenyl70 100 phosphoroamidodithionite S,S di-n-propyl-N-ethyl 100 90 94phosphoroamidodithionite S,S-di-n-butyl-N-acetyl 96 96 94phosphoroamidodithionite S,S-di-nbutyl Npropionyl 98phosphoroamidodithionite S,Sdi-n-propyl-N-acetyl I00 [00 M0phosphoroamidodithionite S,S-di-n-propyl-N-acetyl-Nphenyl lOO 96phosphoroamidodilhionite In general, the preferred compounds for use asinsecticides are those wherein R1 and R, are individually propyl orbutyl, R is hydrogen, methyl, ethyl or propyl and R, is hydrogen,methyl, ethyl, propyl or fluorophenyl; or benzyl or allyl when R, and Rare propyl.

In addition to the specific formulations and application techniquesdescribed above, one or more of the compound derivatives of theinvention may be applied in other liquid or solid formulations to theinsects, their environment, or hosts susceptible to insect attack. Forexample, they may be sprayed or otherwise applied directly to plants orsoil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxicamount of one or more carbamate de rivatives and a biologically inertcarrier. Usually they will also contain a wetting agent. Solid carrierssuch as clay, talc, sawdust and the like may be used in suchformulations. Liquid diluents which may be used with these compoundsinclude water and aromatic solvents. in addition these formulations maycontain other compatible pesticides, plant growth regulators, fillers,stabilizers, attractants and the like.

The concentration of the active ingredient to be used with inertcarriers, either solid or liquid carriers, will be dependent upon manyfactors, such asthe particular carbamate compound which is used, thecarrier in or upon which it is incorporated, the method and conditionsof application, the insect species to be controlled, etc., the properconsideration of these factors being within the skill of these versed inthe art. In general, the toxic ingredients of this invention will beeffective in concentrations from about 0.000] percent by weight to ashigh as 90 percent by weight or higher. Economically, of course, it isdesirable to use lower concentrations of this active ingredient. Thus,it is usually desirable to use less than percent by weight of the activeingredient in a particular composition.

The terms insecticide and insect" as used herein refer to their broadand commonly understood usage rather than to those creatures which inthe strict biological sense are classified as insects. Thus, the terminsect" is used not only to include small invertebrate animals belongingto the class lnsecta but also to other related classes of arthropodswhose members are segmented invertebrates having more or fewer than sixlegs, such as spiders, mites, ticks, centipedes, worms and the like.

Some of the compounds of the present invention are also useful in thecontrol of nematodes and algae, for example Euglena.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion, without departing from the spirit or scope ofthe disclosure or from the scope of the following claims.

I claim:

1. Compound of the formula wherein R, and R are independently alkyl of lto 8 carbon atoms or alkenyl of 2 to 3 carbon atoms, R, is hydrogen oralkyl of l to 4 carbon atoms and R, is acyl of 2 to 4 carbon atoms.

2. The compound of claim 1 wherein R, and R, are independently alkyl ofl to 8 carbon atoms.

3. The compound of claim 1 wherein R and R are independently alkyl of 3to 4 carbon atoms.

4. The compound of claim 1 wherein R, and R, are the same and are alkylof l to 4 carbon atoms and R, is hydrogen.

5. S,S-di-n-butyl-N-acetyl phosphoroamidothioate, according to claim 4.

6. S,S di-n-propyl-N-acetyl phosphoroamidodithionite, according to claim4.

7. S,S-di-i-propyl-N-butyryl phosphoroamidodithionite, according toclaim 4.

8. S,S-di-i-propyl-N-acetyl phosphoroamidodithionite, according to claim4.

9. S,S-di-n-butyl-N-propionyl phosphoroamidodithionite, according toclaim 4.

t i t t l

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1 wherein R1 andR2 are independently alkyl of 1 to 8 carbon atoms.
 3. The compound ofclaim 1 wherein R1 and R2 are independently alkyl of 3 to 4 carbonatoms.
 4. The compound of claim 1 wherein R1 and R2 are the same and arealkyl of 1 to 4 carbon atoms and R3 is hydrogen. 5.S,S-di-n-butyl-N-acetyl phosphoroamidothioate, according to claim
 4. 6.S,S-di-n-propyl-N-acetyl phosphoroamidodithionite, according to claim 4.7. S,S-di-i-propyl-N-butyryl phosphoroamidodithionite, according toclaim
 4. 8. S,S-di-i-propyl-N-acetyl phosphoroamidodithionite, acCordingto claim
 4. 9. S,S-di-n-butyl-N-propionyl phosphoroamidodithionite,according to claim 4.